CN101875602B - Heterogeneous catalytic method for synthesis of isophorone from acetone - Google Patents
Heterogeneous catalytic method for synthesis of isophorone from acetone Download PDFInfo
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- CN101875602B CN101875602B CN 200910083130 CN200910083130A CN101875602B CN 101875602 B CN101875602 B CN 101875602B CN 200910083130 CN200910083130 CN 200910083130 CN 200910083130 A CN200910083130 A CN 200910083130A CN 101875602 B CN101875602 B CN 101875602B
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Abstract
The invention relates to a heterogeneous catalytic method for synthesis of isophorone from acetone. Acetone is used as a raw material, and a magnesium-aluminum composite oxide is used as a catalyst for carrying out catalytic synthesis to obtain isophorone; the magnesium-aluminum composite oxide comprises MgO, Al2O3 and MgAl2O4, the molar ratio of magnesium to aluminum is 0.3-3, the specific surface area is 80-150m<2>/g, and the pore volume is 0.2-0.3cm<3>/g; a fixed bed reactor is used for carrying out synthetic reaction, 20ml of 20 to 40-mesh catalyst is added into a stainless steel reactor of which the inner diameter is 10mm, the reactor is heated to the reaction temperature from the room temperature at the rate of 10 DED C/min after being qualified through an air-tight test, and then, the analytically pure acetone raw material is injected into the reactor by a duplex plunger pump through a preheater; the reaction temperature is 220-290 DEG C; the reaction pressure is normal pressure; and the air speed of the acetone liquid is 0.1-1.0/h, the selectivity reaches 94.5%, the conversion rate reaches 44.8%, and the stability reaches 1000 hours.
Description
Technical field
The present invention relates to green, clean catalysis technical field, specifically refer to a kind of heterogeneous catalytic method by synthesis of isophorone from acetone, wherein use magnesium-aluminium composite oxide to make catalyzer, under the reaction conditions of gentleness, carry out the condensation reaction of acetone gas-solid heterogeneous catalyst.
Background technology
Isophorone is as one of deep processed product of acetone, and development is very fast in developed countries such as American and Britain, moral, days.Along with the fast development of chemical industry especially synthetic resin industry, the demand of isophorone is rapid growth also.Beginning of the nineties late 1980s, external many families were newly-built or extended the isophorone production equipment, the at present production of isophorone mainly concentrates on western developed country and area with consumption, main manufacturer has U.S. Rohm and Haas Company (US) Independenec Mall West, Philadelphia, Pennsy Lvania 1, U.S. combinating carbide company, BP chemical company, Germany dimension Bagong department, Huels AG, Japanese contest Lopa Nationality company, sumitomo chemical company etc., overall throughput is 100,000 t/a.And China there is no producer's suitability for industrialized production isophorone at present, only has several reagent enterprises to produce on a small quantity, such as Shanghai experiment reagent company limited, and the Long Huagongshijichang of Chengdu section etc.; The units such as Shanghai solvent factory, Ji Hua company of PetroChina Company Limited. carry out excessive quantity research work, once have on a small scale pilot plant.But it is blank that the domestic production industrialization still belongs to.
The technique comparatively ripe by synthesis of isophorone from acetone mainly is divided into two kinds: mesityl oxide method and acetone condensation method.Wherein industrialized synthetic method is take acetone condensation method as main.The method of condensation of acetone synthesis of isophorone can be divided into again two kinds by contact condition: a kind of is pressurization liquid phase condensation method in basic solution, and another kind is the heterogeneous catalyst condensation method of solid catalyst.The isophorone total recovery that the liquid phase condensation method obtains is about 60～70%, acetone conversion about 6～10%.It is simple, easy to operate that this method has a catalyzer, isophorone yield advantages of higher, be specially adapted to suitability for industrialized production, but shortcoming can not be ignored, namely reactor is high-tension apparatus, internal structure is complicated, acetone conversion is not high, and production cost is higher, contains a large amount of potassium hydroxide in the waste liquid, not only etching apparatus, separation and aftertreatment are difficult, and the distillation tower operating process is also wayward.In addition, this technique produces high dense strong basicity organic liquid waste, waste water, causes environmental pollution.And development environment close friend's catalyzer and relevant catalysis synthesizing technology thereof more and more cause people's attention.The recent domestic scholar carries out primary study to acetone gas-solid phase preparing isophorone using condensation technique.This method has the acetone conversion height, and catalyzer easily prepares, and reactor is the advantages such as fixed bed, easy amplification.In solid catalyst, the magnalium system receives increasing concern because of its suitable acid-basicity position.Dang Mingyan etc. have prepared magnesium-aluminium composite oxide catalyzer, the highlyest can obtain 19.0% acetone conversion and 47.4% isophorone selectivity.J.I.Cosimo has investigated the impact of Mg-Al hydrotalcite on the condensation reaction of acetone gas-solid phase, the Mg-Al hydrotalcite of finding MgO and roasting to isophorone, mesityl oxide and isomers selectivity thereof near 100%.The author points out that isophorone is to generate under the effect of surface hydroxyl, the magnesium aluminum-hydrotalcite of high Al content is the suitable catalyzer that condensation of acetone prepares isophorone.C.Flego etc. have studied the aldol reaction at the upper acetone of a series of acidic molecular sieves (comprising aperture, hollow, large pore zeolite and micropore, mesoporous amorphous aluminum silicide).The transformation efficiency that the result shows acetone is relevant with B acid acid position on the molecular sieve and increase along with the increase of the sour bit density of molecular sieve.Aristech company has synthesized a kind of Mg-Al composite oxide and has made catalyzer, found that, on this catalyzer, acetone conversion is up to 32.5%, and the isophorone selectivity reaches 74.8%.On the basis of this catalyzer, the said firm has developed again a kind of new catalyzer, adds diatomite, then moulding, drying, roasting in magnesium/aluminium composite anion clay.Evaluation result shows that on this catalyzer, acetone conversion can reach 27.9%, and isophorone adds the mesityl oxide selectivity and reaches 87%, and 1200 hours non-inactivations of catalyzer continuous operation.Although the heterogeneous condensation method of acetone gas-solid has many advantages, from the result of study of present stage, there are the shortcomings such as preparation technology's relative complex, cost height, life-span weak point, regeneration difficulty and isophorone selectivity are low in the catalyzer of developing.So the key of this Technology is that the development activity is high, selectivity is high, the life-span is long, prepare simple Novel solid-catalyst.
Summary of the invention:
The present invention seeks to use magnesium-aluminium composite oxide to make catalyzer, at low temperature, normal pressure and do not add under the mild conditions of any solvent, realize that efficient, highly selective and high stability ground prepare isophorone by the condensation of acetone gas-solid heterogeneous catalyst.
Reaction expression of the present invention is:
The present invention relates to a kind of heterogeneous catalytic method by synthesis of isophorone from acetone.It is characterized in that using acetone as reactant, select a kind of Mg-Al composite oxide as catalyzer, is that 220-290 ℃, reaction pressure are that normal pressure, acetone liquid feeding air speed are 0.1-1.0h in temperature of reaction
-1Condition under carry out.The method reaction conditions is gentle, technical security, and the green low toxicity of technological process, simultaneously, the catalyst system therefor preparation is simple, and cost is low, and selectivity is high, good stability.
According to synthetic method described above, the Mg-Al composite oxide catalyzer is by MgO, Al
2O
3And MgAl
2O
4Form specific surface area of catalyst 80-150m
2/ g, pore volume are 0.2-0.3cm
3/ g.
Concrete preparation method is as follows:
1. get magnesium nitrate and aluminum nitrate is dissolved in distilled water, control Mg/Al mol ratio is 0.3-3, is mixed with magnesium nitrate, the aluminum nitrate mixing salt solution A of 0.1-2 volumetric molar concentration.
2. keep A solution at 38-42 ℃, and under agitation in A solution, dropwise add NH
3.H
2O to pH is worth to 8-11.
3. drip NH
3.H
2After O is complete, A solution is warming up to 60-100 ℃ of aging 3-12 hour.
4. filter after leaving standstill cooling 1-6h.
5. be 7.0-10.0 with deionized water washing leaching cake to filtrate pH value.
6. dried overnight in 80-120 ℃ of baking oven, under air atmosphere 350-700 ℃ roasting 2-7 hour.
According to synthetic method described above, by synthesis of isophorone from acetone reaction, at normal pressure, temperature of reaction 220-290 ℃, acetone solution air speed 0.1-1.0h
-1Operational condition under carry out.Adopt fixed-bed reactor to carry out this building-up reactions, dress 20ml, 20-40 order catalyzer add in the stainless steel reactor of internal diameter 10mm, after gas-tightness test is qualified, with the speed of 10 ℃/min from the room temperature temperature programming to temperature of reaction, again with analytical pure acetone raw material by doubleplunger pump in the preheater injecting reactor.Products therefrom cools off through 0 ℃ cold-trap, collects.Product analysis carries out chromatographic column adopting PEG-20000 capillary column at Shimadzu 2010 gas chromatograph fid detectors.
According to synthetic method described above, by the synthesis of isophorone from acetone heterogeneous catalytic reaction, acetone conversion reaches as high as 44.8%, and the isophorone selectivity reaches as high as 95.4%.This catalyzer also has good stability, and the life-span can reach more than 1000 hours.
The present invention compared with prior art has following advantage:
1. reaction conditions is gentle, technical security, the green low toxicity of technological process.
2. method for preparing catalyst is simple, and is with low cost.
3. catalyzer has highly selective, high stability and higher activity.
Description of drawings
The test of Fig. 1 Mg-Al composite oxide catalyst stability, reaction conditions: 0.1MPa, 290 ℃, 1.0h
-1
Embodiment
Embodiment 1
23.08 gram magnesium nitrate hexahydrates and 56.27 grams, nine water aluminum nitrates are dissolved in the 2000ml deionized water, under 38 ℃, dropwise add ammoniacal liquor to pH be 8.5.70 ℃ of lower constant temperature wore out 12 hours, left standstill cooling 1 hour.Filter and be 7.0 with deionized water drip washing filter cake to filtrate pH value.80 ℃ of lower dried overnight made catalyzer in 7 hours in 350 ℃ of roastings under the air atmosphere.The evaluating catalyst condition is: normal pressure, 220 ℃, acetone feed amount are 0.33ml/mim, and after reaction was carried out 24 hours, sampling was analyzed, and acetone conversion is 20.3%, and the isophorone selectivity is 86.5%.
Embodiment 2
The catalyzer preparation is with embodiment 1.The evaluating catalyst condition is: normal pressure, 250 ℃, acetone feed amount are 0.33ml/mim, and after reaction was carried out 24 hours, sampling was analyzed, and acetone conversion is 25.2%, and the isophorone selectivity is 90.0%.
Embodiment 3
The catalyzer preparation is with embodiment 1.The evaluating catalyst condition is: normal pressure, 290 ℃, acetone feed amount are 0.33ml/mim, and after reaction was carried out 24 hours, sampling was analyzed, and acetone conversion is 34.5%, and the isophorone selectivity is 90.2%.
Embodiment 4
23.08 gram magnesium nitrate hexahydrates and 56.27 grams, nine water aluminum nitrates are dissolved in the 2000ml deionized water, under 38 ℃, dropwise add ammoniacal liquor to pH be 9.0.70 ℃ of lower constant temperature wore out 8 hours, left standstill cooling 4 hours.Filter and be 8.0 with deionized water drip washing filter cake to filtrate pH value.80 ℃ of lower dried overnight made catalyzer in 6 hours in 400 ℃ of roastings under the air atmosphere.The evaluating catalyst condition is: normal pressure, 290 ℃, acetone feed amount are 0.33ml/mim, and after reaction was carried out 24 hours, sampling was analyzed, and acetone conversion is 34.8%, and the isophorone selectivity is 89.5%.
Embodiment 5
The catalyzer preparation is with embodiment 4.The evaluating catalyst condition is: normal pressure, 290 ℃, acetone feed amount are 0.23ml/mim, and after reaction was carried out 24 hours, sampling was analyzed, and acetone conversion is 38.0%, and the isophorone selectivity is 91.4%.
Embodiment 6
The catalyzer preparation is with embodiment 4.The evaluating catalyst condition is: normal pressure, 290 ℃, acetone feed amount are 0.13ml/mim, and after reaction was carried out 24 hours, sampling was analyzed, and acetone conversion is 42.3%, and the isophorone selectivity is 90.0%.
Embodiment 7
The catalyzer preparation is with embodiment 4.The evaluating catalyst condition is: normal pressure, 290 ℃, acetone feed amount are 0.03ml/mim, and after reaction was carried out 24 hours, sampling was analyzed, and acetone conversion is 44.8%, and the isophorone selectivity is 90.5%.
Embodiment 8
269.26 gram magnesium nitrate hexahydrates and 393.90 grams, nine water aluminum nitrates are dissolved in the 1000ml deionized water, under 40 ℃, dropwise add ammoniacal liquor to pH be 9.0.70 ℃ of lower constant temperature wore out 8 hours, left standstill cooling 4 hours.Filter and be 8.0 with deionized water drip washing filter cake to filtrate pH value.80 ℃ of lower dried overnight made catalyzer in 6 hours in 400 ℃ of roastings under the air atmosphere.The evaluating catalyst condition is: normal pressure, 290 ℃, acetone feed amount are 0.33ml/mim, and after reaction was carried out 24 hours, sampling was analyzed, and acetone conversion is 36.3%, and the isophorone selectivity is 88.4%.
Embodiment 9
269.26 gram magnesium nitrate hexahydrates and 393.90 grams, nine water aluminum nitrates are dissolved in the 1000ml deionized water, under 40 ℃, dropwise add ammoniacal liquor to pH be 9.0.100 ℃ of lower constant temperature wore out 3 hours, left standstill cooling 6 hours.Filter and be 8.0 with deionized water drip washing filter cake to filtrate pH value.80 ℃ of lower dried overnight made catalyzer in 3 hours in 600 ℃ of roastings under the air atmosphere.The evaluating catalyst condition is: normal pressure, 290 ℃, acetone feed amount are 0.33ml/mim, and after reaction was carried out 24 hours, sampling was analyzed, and acetone conversion is 36.9%, and the isophorone selectivity is 91.2%.
Embodiment 10
269.26 gram magnesium nitrate hexahydrates and 393.90 grams, nine water aluminum nitrates are dissolved in the 1000ml deionized water, under 40 ℃, dropwise add ammoniacal liquor to pH be 10.0.60 ℃ of lower constant temperature wore out 8 hours, left standstill cooling 4 hours.Filter and be 9.0 with deionized water drip washing filter cake to filtrate pH value.80 ℃ of lower dried overnight made catalyzer in 6 hours in 400 ℃ of roastings under the air atmosphere.The evaluating catalyst condition is: normal pressure, 290 ℃, acetone feed amount are 0.33ml/mim, and after reaction was carried out 24 hours, sampling was analyzed, and acetone conversion is 35.8%, and the isophorone selectivity is 95.4%.
Embodiment 11
269.26 gram magnesium nitrate hexahydrates and 393.90 grams, nine water aluminum nitrates are dissolved in the 1000ml deionized water, under 41 ℃, dropwise add ammoniacal liquor to pH be 10.5.60 ℃ of lower constant temperature wore out 6 hours, left standstill cooling 4 hours.Filter and be 9.0 with deionized water drip washing filter cake to filtrate pH value.120 ℃ of lower dried overnight made catalyzer in 2 hours in 700 ℃ of roastings under the air atmosphere.The evaluating catalyst condition is: normal pressure, 290 ℃, acetone feed amount are 0.33ml/mim, and after reaction was carried out 24 hours, sampling was analyzed, and acetone conversion is 39.6%, and the isophorone selectivity is 89.1%.
Embodiment 12
269.26 gram magnesium nitrate hexahydrates and 393.90 grams, nine water aluminum nitrates are dissolved in the 1000ml deionized water, under 40 ℃, dropwise add ammoniacal liquor to pH be 11.0.60 ℃ of lower constant temperature wore out 6 hours, left standstill cooling 4 hours.Filter and be 10.0 with deionized water drip washing filter cake to filtrate pH value.120 ℃ of lower dried overnight made catalyzer in 3 hours in 600 ℃ of roastings under the air atmosphere.The evaluating catalyst condition is: normal pressure, 290 ℃, acetone feed amount are 0.33ml/mim, and after reaction was carried out 24 hours, sampling was analyzed, and acetone conversion is 29.1%, and the isophorone selectivity is 88.5%.
Embodiment 13
23.08 gram magnesium nitrate hexahydrates and 13.5 grams, nine water aluminum nitrates are dissolved in the 400ml deionized water, under 42 ℃, dropwise add ammoniacal liquor to pH be 11.0.60 ℃ of lower constant temperature wore out 6 hours, left standstill cooling 4 hours.Filter and be 10.0 with deionized water drip washing filter cake to filtrate pH value.120 ℃ of lower dried overnight made catalyzer in 6 hours in 400 ℃ of roastings under the air atmosphere.The evaluating catalyst condition is: normal pressure, 290 ℃, acetone feed amount are 0.33ml/mim, and after reaction was carried out 24 hours, sampling was analyzed, and acetone conversion is 22.3%, and the isophorone selectivity is 80.9%.
Embodiment 14
23.08 gram magnesium nitrate hexahydrates and 13.5 grams, nine water aluminum nitrates are dissolved in the 400ml deionized water, under 40 ℃, dropwise add ammoniacal liquor to pH be 10.0.60 ℃ of lower constant temperature wore out 6 hours, left standstill cooling 4 hours.Filter and be 9.0 with deionized water drip washing filter cake to filtrate pH value.80 ℃ of lower dried overnight made catalyzer in 6 hours in 400 ℃ of roastings under the air atmosphere.The evaluating catalyst condition is: normal pressure, 290 ℃, acetone feed amount are 0.33ml/mim, and after reaction was carried out 24 hours, sampling was analyzed, and acetone conversion is 26.3%, and the isophorone selectivity is 88.6%.
Embodiment 15
23.08 gram magnesium nitrate hexahydrates and 13.5 grams, nine water aluminum nitrates are dissolved in the 400ml deionized water, under 42 ℃, dropwise add ammoniacal liquor to pH be 11.0.60 ℃ of lower constant temperature wore out 3 hours, left standstill cooling 4 hours.Filter and be 7.0 with deionized water drip washing filter cake to filtrate pH value.80 ℃ of lower dried overnight made catalyzer in 3 hours in 600 ℃ of roastings under the air atmosphere.The evaluating catalyst condition is: normal pressure, 290 ℃, acetone feed amount are 0.33ml/mim, and after reaction was carried out 24 hours, sampling was analyzed, and acetone conversion is 19.2%, and the isophorone selectivity is 80.0%.
Embodiment 16
This example has carried out stability test take embodiment 10 catalyzer as research object.The evaluating catalyst condition is: normal pressure, 290 ℃, acetone feed amount are 0.33ml/mim, and sampling analysis is spaced apart 24 hours, always lasts more than 1000 hours.The results are shown in Figure 1.
As seen from Figure 1, on this catalyzer, acetone conversion maintains about 31%, and the isophorone selectivity maintains about 92%, and reaction was gone through 1000 hours, and catalyzer is inactivation not.
Claims (1)
1. the heterogeneous catalytic method by synthesis of isophorone from acetone is characterized in that: do raw material with acetone, make catalyzer with Mg-Al composite oxide, through the heterogeneous catalyst synthesis of isophorone;
Mg-Al composite oxide is by MgO, Al
2O
3And MgAl
2O
4Form, the magnalium mol ratio is 0.3-3, and specific surface area is 80-150m
2/ g, pore volume are 0.2-0.3cm
3/ g;
Adopt fixed-bed reactor to carry out building-up reactions, 20ml, 20-40 order catalyzer are added in the stainless steel reactor of internal diameter 10mm, after gas-tightness test is qualified, speed with 10 ℃/min is warming up to temperature of reaction from room temperature, again with analytical pure acetone raw material by doubleplunger pump in the preheater injecting reactor;
Temperature of reaction is 220-290 ℃;
Reaction pressure is normal pressure;
Acetone liquid air speed is 0.1-1.0h
-1
The preparation method of described magnalium composite oxides is:
1. get magnesium nitrate and aluminum nitrate is dissolved in distilled water, control Mg/Al mol ratio is 0.3-3, is mixed with magnesium nitrate, the aluminum nitrate mixing salt solution A of 0.1-2 volumetric molar concentration;
2. keep A solution at 38-42 ℃, and under agitation in A solution, dropwise add NH
3H
2O to pH is worth to 8-11;
3. drip NH
3H
2After O is complete, A solution is warming up to 60-100 ℃ of aging 3-12 hour;
4. filter after leaving standstill cooling 1-6h;
5. be 7.0-10.0 with deionized water washing leaching cake to filtrate pH value;
6. dried overnight in 80-120 ℃ of baking oven, under air atmosphere 350-700 ℃ roasting 2-7 hour.
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102976910A (en) * | 2011-09-05 | 2013-03-20 | 张锦碧 | Environment-friendly and simple preparation method for synthesizing isophorone from acetone |
| CN104549371B (en) * | 2013-10-22 | 2016-11-23 | 中国石油化工股份有限公司 | Catalyst of preparing isophorone using condensation of acetone and preparation method thereof |
| CN105268422B (en) * | 2014-07-11 | 2018-09-14 | 中国石油化工股份有限公司 | The preparation method of isophorone catalyst |
| CN105126801A (en) * | 2015-08-28 | 2015-12-09 | 厦门大学 | Catalyst used for synthesizing isophorone and preparation method thereof |
| CN106831385B (en) * | 2015-12-03 | 2020-06-09 | 中国石油化工股份有限公司 | Method for preparing isophorone from acetone |
| CN111097397A (en) * | 2018-10-25 | 2020-05-05 | 中国石油化工股份有限公司 | Method for synthesizing mesityl oxide and isophorone |
| KR102477904B1 (en) * | 2020-10-27 | 2022-12-15 | 금호석유화학 주식회사 | Molded catalyst, method of preparing the catalyst, and method for producing cyclic ketone using the same |
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Non-Patent Citations (2)
| Title |
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| 以镁铝水滑石为前驱体制备复合氧化物催化丙酮气相缩合反应;王芳珠等;《无机化学学报》;20080930;第24卷(第9期);1417-1423 * |
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